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EP0838039B9 - Nouveaux materiaux organiques photochromes - Google Patents

Nouveaux materiaux organiques photochromes Download PDF

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Publication number
EP0838039B9
EP0838039B9 EP96921726A EP96921726A EP0838039B9 EP 0838039 B9 EP0838039 B9 EP 0838039B9 EP 96921726 A EP96921726 A EP 96921726A EP 96921726 A EP96921726 A EP 96921726A EP 0838039 B9 EP0838039 B9 EP 0838039B9
Authority
EP
European Patent Office
Prior art keywords
materials according
photochromic
chain transfer
transfer agent
radical polymerization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP96921726A
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German (de)
English (en)
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EP0838039A4 (fr
EP0838039A1 (fr
EP0838039B1 (fr
Inventor
David Henry
Jacques Jean Vial
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Corning Inc
Original Assignee
Corning Inc
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Filing date
Publication date
Priority claimed from FR9508424A external-priority patent/FR2736643B1/fr
Application filed by Corning Inc filed Critical Corning Inc
Publication of EP0838039A1 publication Critical patent/EP0838039A1/fr
Publication of EP0838039A4 publication Critical patent/EP0838039A4/fr
Publication of EP0838039B1 publication Critical patent/EP0838039B1/fr
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Publication of EP0838039B9 publication Critical patent/EP0838039B9/fr
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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • G02B5/23—Photochromic filters
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols

Definitions

  • the invention relates to novel photochromic transparent organic materials with high index of refraction presenting no optical distortion in solid form, a method for their preparation, and the articles made from these materials.
  • the polymer matrix of such a lens should be crosslinked thermally, free of optical distortion in solid form and able to receive appropriate mixtures of photochromic dyes and to be crosslinked in the presence of such appropriate mixtures of photochromic dyes, for example spiroxazines and chromenes, to obtain a material which presents a high initial transmission before exposure and a high capacity for darkening after exposure, all with rapid darkening and lightening kinetics.
  • the material should have a low thermal dependence, a high resistance to fatigue, and as high an index of refraction as possible.
  • This copolymer could be a good polymer matrix for an ophthalmic article, such as a lens.
  • the material obtained is still unsatisfactory, because the photochromic dyes are inhibited by the brominated chain transfer agent used, as has been observed by the present inventors. It is also necessary to later incorporate the dyes into the matrix notably by a specific thermal diffusion method, which increases the cost price of the material and complicates its manufacturing process.
  • a milder radical polymerization initiator such as a diazo compound, for example, azobisisobutyronitrile
  • the present invention is intended to meet this need.
  • the present invention concerns novel ophthalmic transparent organic materials presenting an index of refraction of more than 1.55, which are free of optical distortions and are prepared by radical polymerization of a polymerizable composition comprising:
  • the invention also relates to a method for the preparation of novel photochromic transparent organic materials presenting an index of refraction of more than 1.55, which are free of optical distortions, characterized in that it consists of carrying out a radical polymerization of a polymerizable composition comprising:
  • the polymerizable composition can contain, in addition:
  • the monomers (a) with formula I are well known and commercially available.
  • Styrene and methylstyrene are the monomers (b) with formula II.
  • the monomers (f) with formula III are represented by divinylbenzene and di(methylvinyl)benzene.
  • the kinetic parameters of the final photochromic material can be adjusted as desired: the addition of a monomer (b) such as styrene to the dimethacrylic compound (a), besides having an advantageous effect on the optical properties, also reduces the kinetics of the dyes that would intrinsically be too rapid in the methacrylic matrix.
  • a monomer (b) such as styrene
  • a third monomer (f) such as divinylbenzene
  • the photochromic dye (c) is selected from the general classes of spiroxazines, spiropyrans and chromenes with photochromic properties imparted. A very large number of photochromic dyes of this type have been described in the literature and are commercially available. Usable spiroxazine dyes have been described notably in U.S. Patent Nos.
  • the proportion of the photochromic dyes to be incorporated in the polymerizable composition can range from 0.01 to 1.0 wt%, preferably 0.05-0.5 wt%, with respect to the weight of the monomers.
  • the chain transfer agent (d) is selected from the C 2 -C 16 linear alkanethiols.
  • Linear C 4 -C 16 alkanethiols are preferred, because they are less volatile than the C 2 or C 3 homologs. Specific examples are: butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, decanethiol, dodecanethiol and tetradecanethiol.
  • MEE bis-mercaptoethyl ether
  • the chain transfer agent can be incorporated in the polymerizable composition in the range of 0.1 - 6.0 wt %, advantageously of 100-5,000 ppm, for example, with respect to the monomers.
  • the radical polymerization initiator (e) is selected from the diazo initiator. These compounds are well known and available commercially. Specific examples are azobisisobutyronitrile (AIBN) and 2,2'-azobis(2-methylbutyronitrile) (AMBN), among others. Purely as an indication, a proportion of initiator equivalent to about 0.05-0.5 wt% of the monomers can be incorporated in it.
  • AIBN azobisisobutyronitrile
  • AMBN 2,2'-azobis(2-methylbutyronitrile)
  • the invention concerns the articles made in their entirety or in part of an organic photochromic material according to the invention.
  • examples of such articles are ophthalmic corrective lenses, sun-protection lenses, window glass for vehicles or buildings, etc.
  • the photochromic material of the invention can comprise the entire thickness of the article (solid article), or it can be in the form of a film or a stratified layer applied to a transparent or mineral support.
  • the ophthalmic lenses are the preferred articles, and they can be produced conveniently by carrying out the polymerization in lens molds, for example, as described in U.S. Patent Nos. 2,242,386, 3,136,000 or 3,881,683.
  • the polymerization of the polymerizable composition is conducted in a lens mold under the following conditions: The polymerizable composition is heated slowly until the beginning of the thermal degradation of the diazo compound (e) with release of free radicals. Once the temperature has reached 53°C, it is maintained for 16 hours; then, within 3 hours, the temperature is raised to 90° C, and then maintained for 2 hours. The lens obtained is then removed from the mold.
  • the raw materials used in the examples are the following: Monomers: Diacryl 121 (available from Akzo Chemical) (DIA) Styrene (STY) Divinylbenzene (DVB) ⁇ -Methylstyrene (MST) Catalysts: 2,2'-Azobis-2-methylbutyronitrile (AMBN) Azobisisobutysonitrile (AIBN) Chain transfer agent: Dodecanethiol (according to the invention) (DDT) Tetrabromomethane (comparative example) (TBM) Bis-mercapoethyl ether (MEE) Photochromic dyes: Name Manufacturer Chemical type Blue D (Great Lakes) Spiroxazine Red PNO (Great Lakes) Spiroxazine Yellow L (Great Lakes) Chromene Sea Green (James Robinson Ltd.) Spiroxazine Berry Red (James Robinson Ltd.) Chromene
  • Examples 1-8 show the efficacy of the chain transfer agents (DDT) and (MEE) in eliminating optical distortions (For this purpose only, the examples are provided in polymerizable compositions without photochromic dye).
  • Ex Monomers (g) Chain Transfcr Agent (g) Catalyst Appearance n d DIA STY DVB DDT TBM MEE AMBN (g) AIBN (g) C1 100 - - - 0.4 - 0.2 - Lg distortions 1 557 C2 80 20 - - 0.4 - 0.2 - distortions 1 565 3 80 20 - 0.4 - - 0.2 - no distortions 4 80 10 10 0.4 - - 0.2 - no distortions 1 566 C5 100 - - - - 0 - 0.2 C6 98 - - - - 2 - 0.2 C7 96 - - - 4 - 0.2 C8 94 - - - - 6 - 0.2
  • the indices of refraction of the materials of comparative Examples 1, 2 and Example 4 were, respectively, 1.557, 1.565 and 1.566.
  • the polymerizable composition consisted of Diacryl 121 (80 parts). styrene (20 parts) and AMBN (0.2 part).
  • the polymerizable composition consisted of 100 grams Diacryl 121, 0.2 grams AIBN and no chain transfer agent.
  • the polymerizable composition consisted of 94 grams Diacryl 121; 0.2 grams of AIBN and 6 grams of MEE.
  • T o is the initial transmission of the lens
  • T D15 is the transmission after 15 min of exposure at 20° C under a xenon lamp (thickness of the sample: 2 mm).
  • the polymerizable composition consisted of 80 parts of Diacryl 121, 20 parts of styrene, 0.4 part of DDT and the quantities of initiator and dye indicated in the table below, which also gives the values of To and T D15 .
  • the chain transfer agent (DDT)
  • the polymerizable composition consisted of 80 parts of Diacryl 121, 20 parts of styrene, 0.4 part of AMBN and the percentage of DDT indicated in the table below, which also gives the Shore D hardness of the material obtained.
  • the polymerizable compositions for these examples were prepared without any dyes..
  • the polymerizable composition consisted of 0.2 part of AMBN and 0.4 part of DDT, in addition to the ingredients indicated in the table below which also indicates the Tg (glass transition temperature) and the Shore D hardness of the material obtained.
  • Example DIA STY DVB Tg Shore D Hardness DVB/STY 24 100 0 - 110 - 0 25 95 5 - 112 - 0 26 85 15 - 121 - 0 27 80 20 - 124 - 0 28 90 10 - - 85 0 29 90 10 2 - 86 0.2 30 90 10 4 - 86 0.4 31 90 10 6 - 86-87 0.6 32 90 10 10 - 87 1.0
  • the polymerizable composition consisted of 0.2 part of AMBN, 0.4 part of DDT, 0.015 part of Sea Green dye and 0.30 part of Berry Red dye, in addition to the monomers indicated in the table below, which also indicates the time for half-bleaching of the lenses obtained.
  • the polymerizable composition consisted of 0.2 part of AMBN, 0.4 part of DDT, 0.015 part of Sea Green dye, and 0.30 part of Berry Red dye, in addition to the monomers indicated in the table below, which also indicates the half-bleaching time of the lenses obtained.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Eyeglasses (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
  • Optical Filters (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Claims (20)

  1. Matériaux organiques transparents photochromiques présentant un indice de réfraction supérieur à 1,55 qui sont exempts de distorsions optiques, et préparés par polymérisation radicalaire d'une composition polymérisable comprenant :
    a) 80 à 95 % en poids d'au moins un monomère représenté par la formule générale (I):
    Figure 00220001
    où R = H ou CH3 et m et n sont indépendamment 1 ou 2 ;
    b) 5 à 20 % en poids d'au moins un monomère monovinylique aromatique représenté par la formule générale (II) :
    Figure 00220002
    où R1 = H ou CH3 ;
    c) une quantité efficace d'au moins un colorant conférant au matériau des propriétés photochromiques, choisi dans le groupe des spiroxazines, spiropyranes et chromènes ;
    d) une quantité efficace d'un agent de transfert de chaíne alcanethiol linéaire en C2-C16 ou bis-mercaptoalkyléther ; et
    e) une quantité efficace d'un composé diazoïque comme initiateur de polymérisation radicalaire.
  2. Matériaux selon la revendication 1 où, dans la formule I, R = H et m = n = 2.
  3. Matériaux selon la revendication 1 ou 2, où le monomère monovinylique aromatique est le styrène.
  4. Matériaux selon l'une quelconque des revendications 1 à 3, où la composition polymérisable contient, en outre, jusqu'à 10 % en poids d'un monomère divinylique aromatique représenté par la formule générale (III) :
    Figure 00230001
    où R1 = H ou CH3.
  5. Matériaux selon la revendication 4, où le monomère divinylique aromatique est le divinylbenzène.
  6. Matériaux selon la revendication 4 ou 5, où le rapport du monomère divinylique aromatique au monomère monovinylique aromatique est dans le rapport de 0 à 2.
  7. Matériaux selon les revendications 3 et 5, où le rapport du divinylbenzène au styrène est dans le domaine de 0,2 à 1,0.
  8. Matériaux selon l'une quelconque des revendications 1 à 7, où l'agent de transfert de chaíne (d) est un alcanethiol en C4-C16 ou un bis-mercaptoalkyléther.
  9. Matériaux selon la revendication 8, où l'agent de transfert de chaíne est choisi dans le groupe consistant en le butanethiol, le pentanethiol, l'hexanethiol, l'heptanethiol, l'octanethiol, le décanethiol, le dodécanethiol, le tétradécanethiol et le bis-mercaptoéthyléther.
  10. Matériaux selon l'une quelconque des revendications 1 à 9, où l'agent de transfert de chaíne est présent en une quantité dans le domaine de 0,1-6,0 % en poids.
  11. Matériaux selon l'une quelconque des revendications 1 à 10, caractérisés en ce que la quantité d'agent de transfert de chaíne est dans le domaine de 100 à 5 000 ppm.
  12. Matériaux selon l'une quelconque des revendications 1 à 11, où l'initiateur de polymérisation radicalaire (e) est choisi dans le groupe consistant en l'azobis-isobutyronitrile et le 2,2'-azobis(2-méthylbutyronitrile).
  13. Matériaux selon l'une quelconque des revendications 1 à 12, où la quantité d'initiateur de polymérisation radicalaire (e) est dans le domaine de 0,05 à 0,5 % en poids.
  14. Matériaux selon l'une quelconque des revendications 1 à 13, où la composition polymérisable comprend un mélange de colorants photochromiques, un tel mélange étant capable de conférer une teinte grise ou brune aux matériaux à l'état assombri.
  15. Procédé de préparation de matériaux organiques transparents photochromiques présentant un indice de réfraction d'au moins 1,55, ledit procédé comprenant la polymérisation radicalaire d'une composition polymérisable comprenant :
    a) 80 à 95 % en poids d'au moins un monomère représenté par la formule générale (I) :
    Figure 00240001
    où R = H ou CH3 et m et n sont indépendamment 1 ou 2 ;
    b) 5 à 20 % en poids d'au moins un monomère monovinylique aromatique représenté par la formule générale (II) :
    Figure 00240002
    où R1 = H ou CH3;
    c) une quantité efficace d'au moins un colorant conférant au matériau des propriétés photochromiques, choisi dans le groupe des spiroxazines, spiropyranes et chromènes ;
    d) une quantité efficace d'un agent de transfert de chaíne alcanethiol linéaire en C2-C16 ou bis-mercaptoalkyléther ; et
    e) une quantité efficace d'un composé diazoïque comme initiateur de polymérisation radicalaire.
  16. Procédé selon la revendication 15, où la composition polymérisable comprend, en outre, jusqu'à 10 % en poids d'un monomère divinylique aromatique représenté par la formule générale (III) :
    Figure 00250001
    où R1 = H ou CH3.
  17. Procédé selon la revendication 15 ou 16, où la quantité d'agent de transfert de chaíne est dans le domaine de 100 à 5 000 ppm.
  18. Procédé selon l'une quelconque des revendications 15 à 17, où la quantité d'intiateur de polymérisation radicalaire est dans le domaine de 0,05 à 0,5 % en poids.
  19. Article photochromique comprenant un matériau organique photochromique selon l'une quelconque des revendications 1 à 14.
  20. Article photochromique selon la revendication 19, où ledit article est une lentille ophtalmique ou solaire.
EP96921726A 1995-07-12 1996-06-20 Nouveaux materiaux organiques photochromes Expired - Lifetime EP0838039B9 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR9508424A FR2736643B1 (fr) 1995-07-12 1995-07-12 Nouveaux materiaux organiques photochromiques
FR9508424 1995-07-12
US449295P 1995-09-28 1995-09-28
US4492P 1995-09-28
PCT/US1996/010654 WO1997003373A1 (fr) 1995-07-12 1996-06-20 Nouveaux materiaux organiques photochromes

Publications (4)

Publication Number Publication Date
EP0838039A1 EP0838039A1 (fr) 1998-04-29
EP0838039A4 EP0838039A4 (fr) 1998-09-30
EP0838039B1 EP0838039B1 (fr) 2002-03-13
EP0838039B9 true EP0838039B9 (fr) 2003-09-03

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EP96921726A Expired - Lifetime EP0838039B9 (fr) 1995-07-12 1996-06-20 Nouveaux materiaux organiques photochromes

Country Status (11)

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EP (1) EP0838039B9 (fr)
JP (1) JPH11508943A (fr)
KR (1) KR19990028868A (fr)
CN (1) CN1191609A (fr)
AU (1) AU6286796A (fr)
BR (1) BR9609574A (fr)
CA (1) CA2220149A1 (fr)
DE (1) DE69619823T2 (fr)
ES (1) ES2174079T3 (fr)
MX (1) MX9800335A (fr)
WO (1) WO1997003373A1 (fr)

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EP1194487B1 (fr) 1999-07-02 2005-05-11 PPG Industries Ohio, Inc. Revetement poly(meth)acrylique photochrome
ES2245366T3 (es) * 2000-05-31 2006-01-01 Tokuyama Corporation Composicion endurecible y producto endurecido fotocromico.
US7009032B2 (en) 2002-12-20 2006-03-07 Ppg Industries Ohio, Inc. Sulfide-containing polythiols
DE10344412A1 (de) * 2003-09-25 2005-05-19 Röhm GmbH & Co. KG Polymernetzwerke
US11149107B2 (en) 2004-09-01 2021-10-19 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US20090280709A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US11248083B2 (en) 2004-09-01 2022-02-15 Ppg Industries Ohio, Inc. Aircraft windows
US20090280329A1 (en) 2004-09-01 2009-11-12 Ppg Industries Ohio, Inc. Polyurethanes, Articles and Coatings Prepared Therefrom and Methods of Making the Same
US9598527B2 (en) 2004-09-01 2017-03-21 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US11008418B2 (en) 2004-09-01 2021-05-18 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US9464169B2 (en) 2004-09-01 2016-10-11 Ppg Industries Ohio, Inc. Polyurethanes, articles and coatings prepared therefrom and methods of making the same
US11591436B2 (en) 2004-09-01 2023-02-28 Ppg Industries Ohio, Inc. Polyurethane article and methods of making the same
JP4944193B2 (ja) 2006-05-05 2012-05-30 ピーピージー インダストリーズ オハイオ，インコーポレイテッド チオエーテル官能性ポリチオールオリゴマーから調製される組成物および物品
US9335566B2 (en) 2011-04-13 2016-05-10 Hoya Corporation Photochromic lens for eye glasses
KR20150000842A (ko) * 2013-06-24 2015-01-05 주식회사 케이오씨솔루션 고굴절 광학재료용 중합성 조성물과 이의 광변색성 조성물 및 이들을 이용한 고굴절 광학재료의 제조방법
KR102105717B1 (ko) * 2013-08-08 2020-04-28 주식회사 케이오씨솔루션 고굴절 광학재료용 중합성 조성물 및 고굴절 광학재료의 제조방법

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US4713244A (en) * 1985-08-16 1987-12-15 Bausch & Lomb Incorporated Sustained-release formulation containing an amino acid polymer with a lower alkyl (C1 -C4) polar solvent
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US5552091A (en) * 1993-03-12 1996-09-03 Ppg Industries, Inc. Benzopyran compounds

Also Published As

Publication number Publication date
EP0838039A4 (fr) 1998-09-30
EP0838039A1 (fr) 1998-04-29
KR19990028868A (ko) 1999-04-15
EP0838039B1 (fr) 2002-03-13
MX9800335A (es) 1998-07-31
WO1997003373A1 (fr) 1997-01-30
CN1191609A (zh) 1998-08-26
JPH11508943A (ja) 1999-08-03
BR9609574A (pt) 1999-03-02
CA2220149A1 (fr) 1997-01-30
ES2174079T3 (es) 2002-11-01
DE69619823D1 (en) 2002-04-18
DE69619823T2 (de) 2002-11-14
AU6286796A (en) 1997-02-10

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